Dialkyl-4-hydroxyphenylcarboxylates of tris(hydroxy-alkyl) isocyanurate

ABSTRACT

ESTERS OF TRIS(HYDROXYLALKYL)ISOCYANURATES WITH DIALKYL4-HYDROXYPHENYL CARBOXYLIC ACIDS ARE STABILIZERS OF ORGANIC MATERIAL. THE COMPOUNDS, OF WHICH TRIS(2-(3-(3,5DI-TERT.BUTYL-4-HYDROXYPHENYL)PROPIONYLOXY)-ETHYL)ISOCYANURATE IS A TYPICAL EMBODIMENT, ARE PREPARED THROUGH ESTERIFICATION OF TRIS (2-HYDROXYETHYL)ISOCYANURATE.

United States Patent Ofice 3,707,542

Patented Dec. 26, 1972 caproate; animal and vegetable derived oils andfats such 3,707,542 as linseed oil, animal fat, tallow, lard, peanutoil, cod liver DIALKYL-4-HYDRGXYPHENYLCA oil, castor oil, palm oil, cornoil and cottenseed oil; and DE TRISUHYDROXY'ALKYL) ISOCYANURATEhydrocarbon materials such as gasoline, mineral oil, fuel David H.Steinberg, Bronx, and Martin Dexter, Briarclilf Manor NX. assignors toCiba Geigy Corporation, 011, drying oil, cutting fiurds, waxes, resinsand fatty acids such as soaps. gg ifiggfiwg Feb. 25 1971, Ser. 118,967These triesters can be prepared through esterification I C an 55 /38 oftris(hydroxya1kyl)isocyanurate with a dialkyl-4-hy- US. Cl. 260-248 NS 8Claims droxyphenyl carboxylic acid derivative of the formula:

10 R1 ABSTRACT on THE DISCLOSURE HO (CXKHM) COOH Esters oftris(hydroxyalkyl)isocyanurates with dialkyl- 4-hydroxyphenyl carboxylicacids are stabilizers of or- R ganic material. The compounds, of whichtris{2-[3-(3,5- H di-tert.butyl-4-hydroxyphenyl)propionyloxy]-ethy1}isowherein R1, R2 and are asPreviously defined- This cyanurate i a typical b di are prepared h hderivative can be either the free acid, an acid halidethereesterification of tris (Z-hydroxyethyl) isocyanurate. of such asthe acid chloride or acid bromide, or an acid anhydride thereof. Whenthe free acid is employed, the esterification is preferably conducted inan inert non- DETAILED DESCRIPTION aqueous organic solvent in thepresence of an acid catalyst. An inert non-aqueous organic solvent isalso prefer- The invention described herein pertains to a class of ablyemployed when the acid halide or anhydride is utiorganic triesters whichcan be diagrammatically depicted liZed, together With an acid p r u h astriethylamine by the structural formula: or dimethylaniline.

1 (I) ExH2x) n 2a) O C-N I In the compounds depicted by Formula I, eachof R Other esterification techniques, such as transesterificaand R isthe same or difierent alkyl group of from 1 to non with an alkyl esterof the derivatives of Formula II, 4 carbons, i.e., methyl, ethyl,n-propyl, isopropyl, n-butyl, or utilization of an alkali metal salt ofthese derivatives sec-butyl or tert-butyl. The symbol n may be 1 or 2,thus with a tris(haloalkyl)isocyanurate in a manner known embracing theappropriately substituted phenylacetic acid per Se can also be employed.Thus, for example, the methand phenylpropionic acids esters of tris(hydroxyalkyl) yl ester of the acid depicted by Formula II andtris(hyisocyanurate. The symbol x is an integer from 1 to 6. rdroxyalkyl) isocyanurate are heated in the presence of a These compoundsare stabilizers of organic materials catalyst such as sodium methoxideor dibutyltin oxide wich are otherwise subject to thermo-oxidative and/or acith m val of the methanol thus formed. tinic deterioration. Thus,through the incorporation in Alternatively a tr1s(alkali metal)cyanurateor isocyavarious b t t of f bo t 0,005 to bout 5% (by nurate can bereacted with a haloalkyl ester of the derivai h of one or more of thesend i h r alone tive of Formula II, analogously to the proceduredescribed or in combination with other stabilizers such as dilauryl- In3,249,607 to Taub et al.

thiodipropionate, distearylthiodipropionate, ultraviolet The productobtained according to these procedures light absorbers, and the like,there is observed a significant can e p lfied to the degree desirthrough ti al increase in the stability of the substrate. Suchsubstrates intechnlques Such as recl'ystanllatiofl hr m tography.

The following examples will serve to further illustrate the nature ofthe present invention.

elude synthetic organic polymeric substances, such as vinyl resins,formed from the polymerization of vinyl halides or from thecopolymerization of vinyl halides with unsaturated polymerizablecompounds, e.g., vinyl esters, 0:,[3- EXAMPLE 1 unsaturated hydrocarbonssuch as butadienes and styrene; polyolefins such as polyethylene,polypropylene, polybutylene and polyisoprene, including copolymers ofolefins with other ethylenically unsaturated comonomers; polyurethanesand polyamides such as polyhexamethylene A mixture of 48.3 g. (0.165mole) of methyl 3-(3,5-diadipamide and polycaprolactam; polyesters suchas polytert.butyl-4-hydroxyphenyl)propionate, 13.06 g. (0.05 ethyleneterephthalates; polycarbonates; polyacetals; poly- 65 mole) oftris(Z-hydroxyethyl)isocyanurate and 1.87 g. styrene; polyethyleneoxide;copolymers of the foregoing (0.0075 mole) of dibutyltin oxide is firstheated at 135- Tris{2-[3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionyloxy] ethyl}isocyanurate such as those of high impactpolystyrene containing co- 140 C. under nitrogen for 4 hours, and thenat 130 C./ polymers of butadiene and styrene and those formed by 0.1-0.2mm. for 3 hours. The cooled reaction mixture is the copolymerization ofacrylonitrile, butadiene and/0r next dissolved in 100 ml. of drybenzene, filtered through 600 g. of alumina, and washed with about 1 1.of benzene. The combined filtrate and washings are evaporated understyrene. Other materials which are stabilized by these triesters includelubricating oil of the aliphatic ester type such asdi(2-ethylhexy1)azelate and pentaerythritol tetravacuum and the product(48.3 g.) is further purified EXAMPLE 2 Tris{2-[3-(3-methyl-4-hydroxy-5-tert.butylphenyl) propionyloxy] ethyl}isocyanurateFollowing the procedure of Example 1, 43.7 g. of ethyl 3-(3-methyl-5'-tbutyl 4' hydroxyphenyl)propionate, 13.06 g. oftris(2-hydroxyethyl)isocyanurate and 1.87 g. of dibutyltin oxide werereacted. 45 g. of the product was obtained which was purified by passinga benzene solution of the product through alumina. The purified materialwas a glass which melted around 70 C.

EXAMPLE 3 Tris{2-[3-(3,5-dimethyl-4-hydroxyphenyl) propionyloxy]ethyl}isocyanurate A mixture of 20.3 g. of3-(3,5-dimethyl-4-hydroxyphenyl)propionic acid, 8.36 g. oftris(2-hydroxyethyl)isocyanurate, 1.72 g. of toluenesulfonic acidmonohydrate and 150 ml. of toluene was heated for 4 hours at reflux withcontinuous stirring. The reaction mixture was then cooled, washed withwater, 6% sodium carbonate and water again until neutral. The solutionwas dried over molecular sieves, followed by removal of the solventunder vacuum. The residue was a substantially pure product which weight25.1 g. After drying at 100 C. at 0.1 mm. the following analysis wasobtained: Calc. for

(percent): C, 63.87; H, 6.51; N, 5.32. Found (percent):

C, 63.81; H, 6.40; N, 5.10. When the above procedure is repeatedemploying 3- (3,6-di-t-butyl-4-hydroxyphenyl)propionic acid as the acidreactant, the producttris{2-[3-(3,6-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}isocyanurate is obtained.

EXAMPLE 4 Tris{2- 3- (3 methyl-4-hydroxyphenyl) propionyloxy]ethyl}isocyanurate (percent): C, 62.64; H. 6.07; N, 5.62. Found C, 2, H,60.5; N, 5.58.

(percent) 7 EXAMPLE 5 Tris{6-[3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy] hexyl}isocyanurate A mixture of 19.4 g. of trisodiumcyanurate, 536.1 g. of 6-chloro-1-hexanol acetate and 600 g. ofdimethylacetamide are heated for about 20 hours at about C. Then thereaction mixture is cooled to 50 C. and filtered. After thepurification, tris-(6-acetoxyhexyl)isocyanurate is obtained.

The intermediate prepared above is hydrolyzed by sodium hydroxide inaqueous methanol to give tris(6-hydroxyhexyl)-isocyanurate. This productis then reacted with 3-(3,S-di-t-butyl-4-hydroxyphenyl)propionic acidaccording to the producedure of Example 3 yielding the above namedproduct.

[EXAMPLE 6 Tirs{ [3 (3 6-di-t-butyl-4-hydroxyphenyl) -propionyloxy]methyl}isocyanurate One mole of tris (hydroxymethyl)isocyanurate isreacted with 3 moles of 3-(3,S-di-t-butyl-4-hydroxyphenyl) propionylchloride in benzene in the presence of 3 moles of dry pyridine. Thereaction mixture is then filtered and the solvent stripped under reducedpressure to afford the above-named product.

The preparation of tris (hydroxymethyl)isocyanurate is disclosed inPazenko et al., Ukr. Khim. Zh. Vol. 30(2), -8 (1964), Chem. Abst. 61,1866d (1964).

EXAMPLE 7 Tris{2- [3-(3,5-di-t-butyl-4-hydroxyphenyl) -propionyloxy]propyl}isocyanurate A mixture 19.4 g. of trisodium cyanurate, 39.1 g. of1-chloro-2-propanol acetate and 600 g. of dimethylacetamide is reactedaccording to the procedure of Example 5. The intermediate productobtained is tris(2-hydroxypropyl)isocyanurate. This material is reactedwith 3-(3,5- di-t-butyl-4-hydroxyphenyl)propionyl chloride according tothe procedure of Example 6 yielding tris{2-[3-(3,5- di-t-butyl 4hydroxyphenyl)propionyloxy]-propyl}isocyanurate.

What is claimed is:

1. A compound of the formula:

wherein each of R and R independently is a (lower) alkyl group of fromone to four carbon atoms and R is also hydrogen, n has a value of 1 or2, and x has a. value of from 1 to 6.

2. A compound according to claim 1 where each of R and R is methyl ortert.buty1.

3. The compound according to claim 2 which is tris{2- [3-(3,5 ditert.butyl 4 hydroxyphenyl)propionyloxy]ethyl}isocyanurate.

4. The compound according to claim 2 which is tris[2- (3,5 di tert.butyl4 hydroxyphenylacetoxy)ethyl]- isocyanurate.

5. The compound according to claim 2 which is tris{2- [3-(3,5dimethyl-4-hydroxyphenyl)propionyloxy] ethyl} isocyanurate.

6. The compound according to claim 2 which is tris{2- References Cited[3-(3 methyl 4 hydroxyphenyl)propionyloxy]ethyl} UNITED STATES PATENTSisocyanurate.

7. The compound according to claim 2 which is tris{6- gai [3-(3,5 di tbutyl 4 hydroxyphenyl)propionyloxy} 5 W JOHN M. FORD, Primary Examiner8. The compound according to cla1m 2 WhlCh 1s trls- U S 1 XR {{3 (3,5 dit butyl 4 hydroxyphenyDpropionyl- C oxy]methyl}isocyanurate. 99-163;25251.5 R, 403; 26045.8 N

